Benzohydroximoylazole derivatives and insecticide including the same

ABSTRACT

The present invention provides benzohydroximoylazole derivatives represented by the following novel formula: ##STR1## wherein R is a branched alkyl group having not fewer than 5 carbon atoms, a fluorine-substituted alkyl group having not fewer than 2 carbon atoms, a branched alkoxy group having not fewer than 3 carbon atoms, a halogen-substituted alkoxy group having not fewer than 3 carbon atoms, a cycloalkyl group, a cycloalkylmethyl group which may be substituted with one or two alkyl groups, a substituted silylalkyl group, a substituted silylalkyloxy group, a cycloalkyloxy group which may be substituted with one or two alkyl groups, an alkylthio group, a halogen-substituted alkyloxyalkyl group, an alkynyl group, or a halogen-substituted alkenyloxy group; 
     X is a hydrogen atom, a chlorine atom, or a fluorine atom; 
     Y is an alkyl group; and Z is a nitrogen atom or a methyne group, 
     and methods for producing the same, insecticides including the benzohydroximoylazole derivatives as an active ingredient.

RELATED APPLICATIONS

This application was filed as PCT application No. PCT/JP91/01614 on Nov. 25, 1991.

1. Field of the Invention

The present invention relates to a benzohydroximoylazole derivative and to an insecticide containing the same as an active ingredient.

2. Background of the Invention

Heretofore, it has been known that compounds such as 1-(O-ethyl-4-butylbenzohydroximoyl)-1H-1,2,4-triazole and the like have insecticidal activities (for example, as described in Japanese Patent Application First Publication No. 1-308260).

Disclosure of the Invention

Such compounds disclosed in the above-mentioned patent application do not have the sufficient insecticidal effect. Recently, strains of harmful insects exhibiting resistance to conventional insecticides have appeared due no extensive and prolonged use thereof, and for this reason, the effectiveness of conventional insecticides are being lowered. In particular, the harmful insects in the order hemiptera such as the Delphacidae, Deltocephalidae, Aphididae, Pseudococcidae, Aleyrodidae, Pentatomidae, and the like have caused considerable damage to trees and to crops such as rice, wheat, potatoes, and the like.

Therefore, it is desirable to develop an insecticide having both superior insecticidal effect at low rates of application and effectiveness against the resistant strains of harmful insects described above.

The present inventors have synthesized various benzohydroximoylazole derivatives and have carried out extensive research in connection with the physiological activities thereof. As a result, they have found that the compounds according to the present invention wherein special substituents are bonded to the phenyl rings of the benzohydroximoylazole derivatives have extremely superior insecticidal activities against the various harmful insects, especially the harmful hemiptera such as Delphacidae, Deltocephalidae, Aphididae, Pentatomidae, and the like. The insecticidal activities of the compounds according to the present invention are superior to those of the compounds disclosed in Japanese Patent Application First Publication No. 1-308260. In addition, the compounds of the present invention exhibit improved insecticidal activities against the harmful resistant insects described above.

The present invention provides the following benzohydroximoylazol derivatives represented by formula [I] and an insecticide including the same as an active ingredient: ##STR2## wherein R is a branched alkyl group having not fewer than 3 carbon atoms, a fluorine-substituted alkyl group having not fewer than 2 carbon atoms, a branched alkoxy group having not fewer than 3 carbon atoms, a halogen-substituted alkoxy group having not fewer than 3 carbon atoms, a cycloalkyl group, a cycloalkylmethyl group which may be substituted with one or two alkyl groups, a substituted silylalkyl group, a substituted silylalkyloxy group, a cycloalkyloxy group which may be substituted with one or two alkyl groups, an alkylthio group, a halogen-substituted alkyloxyalkyl group, an alkynyl group, or a halogen-substituted alkenyloxy group;

X is a hydrogen atom, a chlorine atom, atom;

Y is an alkyl group; and

Z is a nitrogen atom or a methyne group.

In formula [I], a branched alkyl group having not fewer than 3 carbon atoms includes, for example, isopropyl, isobutyl, s-butyl, t-butyl, isopentyl, 1-methylbutyl, 2-methylbutyl, neopentyl, isohexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 5-methylhexyl, 3,3-dimethylpentyl, 4,4-dimethylpentyl, 1,3,3-trimethylbutyl, 2,3,3-trimethylbutyl, 3,3-dimethylhexyl, 1,1,3,3-tetramethylbutyl, or the like.

A branched alkoxy group having not fewer than 3 carbon atoms includes, for example, isopropoxy, isobutoxy, s-butoxy, t-butoxy, i-pentyloxy, neopentyloxy, 1-methylbutoxy, 2-methylbutoxy, 1,2-dimethylpropoxy, 2-ethylbutoxy, 2,2-dimethylbutoxy, 3,3-dimethylbutoxy, 2,3,3-trimethylpropoxy, 2,2-dimethylpentyloxy, 1,3,3-trimethylbutoxy, 1-ethyl-2,2-dimethylpropoxy, 1-isopropoxy-2-methylpropoxy, or the like.

A fluorine-substituted alkyl group having not fewer than 2 carbon atoms includes, for example, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluoroisopentyl, 4,4,4-trifluoro-3,3-bis(trifluoromethyl)butyl, or the like.

A halogen-substituted alkoxy group having not fewer than 3 carbon atoms includes, for example, 4,4,4-trifluorobutoxy, 3-chloro-2,2-dimethylpropoxy, 1,1,2,3,3,3-hexafluoropropoxy, 2,2-bis(trifluoromethyl)propoxy, 3,3,3-trifluoro-2,2-bis(trifluoromethyl)propoxy, 2,2,3,3,4,4,4-heptafluoro-1-methylbutoxy, or the like.

As a cycloalkyl group, cyclopropyl, cyclopentyl, cyclohexyl, or cycloheptyl may be employed.

A cycloalkylmethyl group which may be substituted with one or two alkyl groups includes cyclopropylmethyl, cyclopentylmethyl, 2-methylcyclopentylmethyl, 3-methylcyclopentylmethyl, cyclohexylmethyl, or 3, 5-dimethylcyclohexylmethyl.

As a substituted silylalkyl group, trialkylsilylalkyl may be employed.

A substituted silylalkyloxy group includes trialkylsilylalkyloxy, dialkylmonoalkenylsilylalkyloxy, or dialkylmonochloro-substituted alkylsilylalkyloxy.

A cycloalkyloxy group which may be substituted with one or two alkyl groups includes cyclopropyloxy, cyclopentyloxy, 2-methylcyclohexyloxy, 3-methylcyclohexyloxy, 4-methylcyclohexyloxy, 2,3-dimethylcyclohexyloxy, or 2,5-dimethylcyclohexyloxy.

As an alkylthio group, 2-methylpropylthio or the like is employed.

A halogen-substituted alkyloxyalkyl group includes 1,1-bis(trifluoromethyl)ethoxymethyl or the like.

As an alkynyl group, 3,3-dimethyl-1-butynyl or the like is used.

An alkenyl group includes 3,3-dimethyl-1-butenyl or 1-hexenyl.

A halogen-substituted alkenyloxy group includes 2-bromo-1-chlorovinyloxy or the like.

In addition, an alkyl group employed in Y includes a linear or branched alkyl group having 1 to 4 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, a t-butyl group, or the like.

In formula [I], it is preferable that R be a branched alkyl group having 3 to 8 carbon atoms, a branched alkoxy group having 3 to 7 carbon atoms, or a halogen-substituted alkoxy group having 3 to 7 carbon atoms; Y be an ethyl group, a propyl group; an isopropyl group, or a s-butyl group; and Z be a nitrogen atom.

The benzohyroximoylazole derivative represented by formula [I] includes two stereomers: syn and anti configurations. The compounds according to the present invention include not only each stereomer but also a mixture of the two stereomers in any ratio.

In addition, in the case where X in formula [I] has a saturated or unsaturated cycloparaffin group or an aliphatic hydrocarbon group in the substituent, there are the possibility that the compound represented by formula [I] has at least two stereomers. The present invention includes these steromers.

Next, the compounds according to the present invention are listed in Table 1. The compound Nos. given in Table 1 will be referred to in the subsequent description.

                                      TABLE 1                                      __________________________________________________________________________      ##STR3##                                                                                                      Melting                                                                        point (°C.) or                          Compound                        Refractive                                     No.   R               X  Y   Z  index (n.sub.D.sup.20)                         __________________________________________________________________________     1     3-C.sub.5 H.sub.11 -i                                                                          4-F                                                                               C.sub.3 H.sub.7 -i                                                                 N  1.5253                                         2     3-OC.sub.3 H.sub.7 -i                                                                          H  C.sub.3 H.sub.7 -i                                                                 N  1.5390                                         3     3-OC.sub.4 H.sub.9 -i                                                                          H  C.sub.3 H.sub.7 -i                                                                 N  1.5341                                         4     3-OC.sub.4 H.sub.9 -s                                                                          H  C.sub.3 H.sub.7 -i                                                                 N  1.5320                                         5     3-OCH(CH.sub.3)CH.sub.2 CH.sub.2 CH.sub.3                                                      H  C.sub.3 H.sub.7 -i                                                                 N  1.5312                                         6     3-OCH.sub.2 CH(CH.sub.3)CH.sub.2 CH.sub.3                                                      H  C.sub.3 H.sub.7 -i                                                                 N  1.5177                                         7     3-OC.sub.5 H.sub.11 -i                                                                         H  C.sub.3 H.sub.7 -i                                                                 N  1.5341                                         8     3-C.sub.4 H.sub.9 -i                                                                           H  C.sub.3 H.sub.7 -i                                                                 N  1.5360                                         9     3-C.sub.5 H.sub.11 -i                                                                          H  C.sub.3 H.sub.7 -i                                                                 N  1.5317                                         10    3-C.sub.4 H.sub.9 -s                                                                           H  C.sub.3 H.sub.7 -i                                                                 N  1.5338                                         11    3-CH.sub.2 CH(CH.sub.3)CH.sub.2 CH.sub.3                                                       H  C.sub.3 H.sub.7 -i                                                                 N  1.5370                                         12    3-C.sub.3 H.sub.7 -i                                                                           H  C.sub.3 H.sub.7 -i                                                                 N  1.5398                                         13    3-C.sub.4 H.sub.9 -t                                                                           H  C.sub.3 H.sub.7 -i                                                                 N  1.5312                                         14    3-OCH.sub.2 CH(C.sub.2 H.sub.5).sub.2                                                          H  C.sub.3 H.sub.7 -i                                                                 N  1.5328                                         15    3-CH(CH.sub.3)CH.sub.2 CH.sub.2 CH.sub.3                                                       H  C.sub.3 H.sub.7 -i                                                                 N  1.5317                                         16    3-CH.sub.2 CH(CH.sub.3)CH.sub.2 CH.sub.2 CH.sub.3                                              H  C.sub.3 H.sub.7 -i                                                                 N  1.5309                                         17    3-CH(CH.sub.3)CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                              H  C.sub.3 H.sub.7 -i                                                                 N  1.5205                                         18    3-CH.sub.2 CH.sub.2 CH(CH.sub.3)CH.sub.2 CH.sub.3                                              H  C.sub.3 H.sub.7 -i                                                                 N  1.5293                                         19    3-OCH.sub.2 CH.sub.2 C(CH.sub.3).sub.3                                                         H  C.sub.3 H.sub.7 -i                                                                 N  1.5289                                         20    3-CH.sub.2 CH(CH.sub.3)CH(CH.sub.3).sub.2                                                      H  C.sub.3 H.sub.7 -i                                                                 N  1.5304                                         21    3-C.sub.5 H.sub.11 -i                                                                          2-F                                                                               C.sub.3 H.sub.7 -i                                                                 N  1.5202                                         22    3-C.sub.5 H.sub.11 -i                                                                          4-F                                                                               C.sub.3 H.sub.7 -i                                                                 N  1.5211                                         23    5-C.sub.5 H.sub.11 -i                                                                          2-F                                                                               C.sub.3 H.sub.7 -i                                                                 N  1.5202                                         24    3-C.sub.6 H.sub.13 -i                                                                          H  C.sub.3 H.sub.7 -i                                                                 N  1.5198                                         25    5-C.sub.5 H.sub.11 -i                                                                          2-Cl                                                                              C.sub.3 H.sub.7 -i                                                                 N  1.5360                                         26    3-OCH(CH.sub.3)CF.sub.2 CF.sub.2 CF.sub.3                                                      H  C.sub.3 H.sub.7 -i                                                                 N  1.4760                                         27    5-OCH(CH.sub.3)CF.sub.2 CF.sub.2 CF.sub.3                                                      2-Cl                                                                              C.sub.3 H.sub.7 -i                                                                 N  1.4919                                         28    5-C.sub.6 H.sub.13 -i                                                                          2-Cl                                                                              C.sub.3 H.sub.7 -i                                                                 N  1.5252                                         29    3-OCH(CH.sub.3)CH.sub.2 C(CH.sub.3).sub.3                                                      H  C.sub.3 H.sub.7 -i                                                                 N  1.5108                                         30    3-C(CH.sub.3).sub.2 CH.sub.2 C(CH.sub.3).sub.3                                                 H  C.sub.3 H.sub.7 -i                                                                 N  1.5230                                         31    3-C.sub.7 H.sub.15 -i                                                                          4-F                                                                               C.sub.3 H.sub.7 -i                                                                 N  1.5147                                         32    3-C.sub.5 H.sub.11 -i                                                                          4-F                                                                               C.sub.3 H.sub.7 -i                                                                 CH 1.5258                                         33    3-C.sub.6 H.sub.13 -i                                                                          4-F                                                                               C.sub.3 H.sub.7 -i                                                                 N  1.5132                                         34    3-C.sub.6 H.sub. 13 -i                                                                         4-F                                                                               C.sub.3 H.sub.7 -i                                                                 CH 1.5230                                         35    3-OC.sub.4 H.sub.9 -i                                                                          H  C.sub.3 H.sub.7 -i                                                                 CH 1.5400                                         36    3-OC.sub.5 H.sub.11 -i                                                                         H  C.sub.3 H.sub.7 -i                                                                 CH 1.5358                                         37    3-CH.sub.2 C(CH.sub.3).sub.3                                                                   H  C.sub.3 H.sub.7 -i                                                                 N  1.5248                                         38    3-OC.sub.4 H.sub.9 -t                                                                          H  C.sub.3 H.sub.7 -i                                                                 N  1.5308                                         39    5-C.sub.6 H.sub.13 -i                                                                          2-F                                                                               C.sub.3 H.sub.7 -i                                                                 N  1.5162                                         40    5-C.sub.6 H.sub.13 -i                                                                          2-F                                                                               C.sub.3 H.sub.7 -i                                                                 CH 1.5225                                         41    3-C.sub.5 H.sub.11 -i                                                                          H  CH.sub.3                                                                           N  1.5422                                         42    3-C.sub.5 H.sub.11 -i                                                                          H  C.sub.4 H.sub.9 -s                                                                 N  1.5293                                         43    3-C.sub.5 H.sub.11 -i                                                                          H  C.sub.2 H.sub.5                                                                    N  1.5326                                         44    3-OCH.sub.2 C(CH.sub.3).sub.3                                                                  H  C.sub.3 H.sub.7 -i                                                                 N  1.5202                                         45    3-C.sub.5 H.sub.11 -i                                                                          H  C.sub.4 H.sub.9                                                                    N  1.5290                                         46    3-CH.sub.2 CH.sub.2 C(CH.sub.3).sub.3                                                          H  C.sub.3 H.sub.7 -i                                                                 N  1.5258                                         47    3-OCH.sub.2 C(CH.sub.3).sub.2 CH.sub.2 CH.sub.3                                                H  C.sub.3 H.sub.7 -i                                                                 N  1.5269                                         48    3-C.sub.5 H.sub.11 -i                                                                          H  C.sub.3 H.sub.7                                                                    N  1.5320                                         49    3-OCF.sub.2 CHFCF.sub.3                                                                        H  C.sub.3 H.sub.7 -i                                                                 N  1.4809                                         50    3-OCH.sub.2 C(CH.sub.3).sub.3                                                                  H  C.sub.3 H.sub.7 -i                                                                 CH 1.5340                                         51    3-OCH(CH.sub.3)C(CH.sub.3).sub.3                                                               H  C.sub.3 H.sub.7 -i                                                                 N  1.5273                                         52    3-OCH.sub.2 C(CH.sub.3).sub.3                                                                  H  C.sub.2 H.sub.5                                                                    N  1.5372                                         53    3-OCH.sub.2 C(CH.sub.3).sub.3                                                                  H  C.sub.4 H.sub.9 -s                                                                 N  1.5276                                         54    3-C.sub.6 H.sub.13 -i                                                                          2-F                                                                               C.sub.3 H.sub.7 -i                                                                 N  1.5173                                         55    3-CH.sub.2 CH.sub.2 CH.sub.2 C(CH.sub.3).sub.3                                                 H  C.sub.3 H.sub.7 -i                                                                 N  1.5255                                         56    3-OCH.sub.2 CH.sub.2 CH.sub.2 CF.sub.3                                                         H  C.sub.3 H.sub.7 -i                                                                 N  1.5088                                         57    3-C.sub.5 H.sub.11 -i                                                                          H  C.sub.4 H.sub.9 -i                                                                 N  1.5288                                         58    3-CH.sub.2 CH.sub.2 CH.sub.2 C(CH.sub.3).sub.3                                                 H  C.sub.4 H.sub.9 -s                                                                 N  1.5229                                         59    3-CH.sub.2 CH.sub.2 CH.sub.2 C(CH.sub.3).sub.3                                                 H  C.sub.3 H.sub.7                                                                    N  1.5268                                         60    3-OCH.sub.2 C(CH.sub.3).sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                       H  C.sub.3 H.sub. 7 -i                                                                N  1.5271                                         61    3-OCH.sub.2 C(CH.sub.3).sub.3                                                                  H  C.sub.3 H.sub.7                                                                    N  45˜46                                    62    3-CH.sub.2 CH.sub.2 C(CH.sub.3).sub.3                                                          H  C.sub.4 H.sub.9 -s                                                                 N  1.5261                                         63    3-CH.sub.2 CH.sub.2 C(CH.sub.3).sub.3                                                          H  C.sub.2 H.sub.5                                                                    N  1.5347                                         64    3-CH.sub.2 CH.sub.2 C(CH.sub.3).sub.3                                                          H  C.sub.4 H.sub.9 -s                                                                 CH 1.5313                                         65    3-CH.sub.2 CH.sub.2 C(CH.sub.3).sub.3                                                          H  C.sub.2 H.sub.5                                                                    CH 1.5401                                         66    3-OCH.sub.2 C(CH.sub.3).sub.2 CH.sub.2 Cl                                                      H  C.sub.3 H.sub.7 -i                                                                 N  1.5440                                         67    3-CH.sub.2 CH.sub.2 C(CH.sub.3).sub.3                                                          H  C.sub.3 H.sub.7                                                                    N  1.5305                                         68    3-CH.sub.2 CH.sub.2 C(CH.sub.3).sub.3                                                          4-F                                                                               C.sub.3 H.sub.7 -i                                                                 N  1.5183                                         69    3-CH.sub.2 CH.sub.2 C(CH.sub.3).sub.3                                                          H  C.sub.4 H.sub.9 -t                                                                 N  1.5238                                         70    3-OCH.sub.2 C(CH.sub.3).sub.2 CH.sub.2 CH.sub.3                                                H  C.sub.3 H.sub.7                                                                    N  1.5290                                         71    3-CH.sub.2 CH.sub.2 C(CH.sub.3).sub.3                                                          H  C.sub.3 H.sub.7 -i                                                                 CH 1.5326                                         72    3-OCH.sub.2 C(CH.sub.3).sub.2 CH.sub.2 CH.sub.2 CH.sub.                                        H  C.sub.3 H.sub.7                                                                    N  1.5300                                         73    3-OCH(CH.sub.3)C(CH.sub.3).sub.3                                                               H  C.sub.3 H.sub.7                                                                    N  1.5327                                         74    3-CH.sub.2 CH.sub.2 C(CH.sub.3).sub.2 CH.sub.2 CH.sub.2 CH.sub.3                               H  C.sub.3 H.sub.7                                                                    N  1.5249                                         75    5-CH.sub.2 CH.sub.2 C(CH.sub.3).sub.2 CH.sub.2 CH.sub.3                                        2-F                                                                               C.sub.3 H.sub.7                                                                    N  1.5233                                         76    3-CH.sub.2 CH.sub.2 C(CH.sub.3).sub.3                                                          4-F                                                                               C.sub.3 H.sub.7                                                                    N  1.5171                                         77    3-OCH.sub.2 C(CH.sub.3).sub.3                                                                  4-F                                                                               C.sub.3 H.sub.7                                                                    N  1.5203                                         78    3-CH.sub.2 C(CH.sub.3).sub.2 CH.sub.2 CH.sub.3                                                 H  C.sub.3 H.sub.7 -i                                                                 N  1.5306                                         79    5-CH.sub.2 CH.sub.2 C(CH.sub.3).sub.3                                                          2-F                                                                               C.sub.3 H.sub.7 -i                                                                 N  1.5168                                         80    3-C.sub.5 H.sub.11 -i                                                                          4-F                                                                               C.sub.3 H.sub.7                                                                    N  1.5214                                         81    3-C.sub.5 H.sub.11 -i                                                                          4-F                                                                               C.sub.2 H.sub.5                                                                    N  1.5262                                         82    3-OCH.sub.2 C(CH.sub.3).sub.3                                                                  4-F                                                                               C.sub.3 H.sub.7 -i                                                                 N  1.5198                                         83    5-CH.sub.2 CH.sub.2 C(CH.sub.3).sub.3                                                          2-F                                                                               C.sub.3 H.sub.7                                                                    N  1.5068                                         84    3-OCH(CH.sub.3)CH.sub.2 CH(CH.sub.3).sub.2                                                     H  C.sub.3 H.sub. 7 -i                                                                N  1.5262                                         85    3-OCH(CH.sub.3)CH.sub.2 CH(CH.sub.3).sub.2                                                     H  C.sub.3 H.sub.7                                                                    N  1.5293                                         86    3-OCH(CH.sub.3)CH(CH.sub.3).sub.2                                                              H  C.sub.3 H.sub.7 -i                                                                 N  1.5327                                         87    5-CH.sub.2 CH.sub.2 C(CH.sub.3).sub.3                                                          2-Cl                                                                              C.sub.3 H.sub.7 -i                                                                 N  1.5292                                         88    5-CH.sub.2 CH.sub.2 C(CH.sub.3).sub.3                                                          2-Cl                                                                              C.sub.3 H.sub.7                                                                    CH 1.5360                                         89    3-OCH(CH.sub.3)CH(CH.sub.3).sub.2                                                              H  C.sub.3 H.sub.7                                                                    N  1.5352                                         90    3-CH.sub.2 CH.sub.2 C(CH.sub.3).sub.3                                                          4-Cl                                                                              C.sub.3 H.sub.7 -i                                                                 N  1.5338                                         91    5-CH.sub.2 CH.sub.2 C(CH.sub.3).sub.3                                                          2-F                                                                               C.sub.3 H.sub.7                                                                    CH 1.5233                                         92    3-CH(CH.sub.3)CH.sub.2 C(CH.sub.3).sub.3                                                       H  C.sub.3 H.sub.7 -i                                                                 N                                                 93    3-CH(CH.sub.3)CH.sub.2 C(CH.sub.3).sub.3                                                       H  C.sub.3 H.sub.7                                                                    N                                                 94    3-CH.sub.2 CH(CH.sub.3)C(CH.sub.3).sub.3                                                       H  C.sub.3 H.sub.7 -i                                                                 N                                                 95    3-CH.sub.2 CH(CH.sub.3)C(CH.sub.3).sub.3                                                       H  C.sub.3 H.sub.7                                                                    N                                                 96    3-CH.sub.2 CH.sub.2 C(CH.sub.3).sub.2 CH.sub.2 CH.sub.3                                        H  C.sub.3 H.sub.7 -i                                                                 N                                                 97    3-CH.sub.2 CH.sub.2 C(CF.sub.3).sub.3                                                          H  C.sub.3 H.sub.7 -i                                                                 N                                                 98    5-CH.sub.2 CH.sub.2 C(CF.sub.3).sub.3                                                          2-F                                                                               C.sub.3 H.sub.7 -i                                                                 N                                                 99    3-OCH(C.sub.2 H.sub.5)C(CH.sub.3).sub.3                                                        H  C.sub.3 H.sub.7                                                                    N  1.5305                                         100   3-OCH(C.sub.2 H.sub.5)C(CH.sub.3).sub.3                                                        H  C.sub.3 H.sub.7 -i                                                                 N  1.5274                                         101   3-OCH.sub.2 C(CH.sub.3)(CF.sub.3).sub.2                                                        H  C.sub.3 H.sub.7                                                                    N                                                 102   3-OCH.sub.2 C(CH.sub.3)(CF.sub.3).sub.2                                                        H  C.sub.3 H.sub.7 -i                                                                 N  1.4852                                         103   3-OCH.sub.2 C(CF.sub.3).sub.3                                                                  H  C.sub.3 H.sub.7                                                                    N                                                 104   3-OCH.sub.2 C(CF.sub.3).sub.3                                                                  H  C.sub.3 H.sub.7 -i                                                                 N                                                 105   5-OCH.sub.2 C(CH.sub.3).sub.3                                                                  2-F                                                                               C.sub.3 H.sub.7                                                                    N                                                 106   5-OCH.sub.2 C(CH.sub.3).sub.3                                                                  2-F                                                                               C.sub.3 H.sub.7 -i                                                                 N                                                 107   5-OCH.sub.2 C(CH.sub.3)(CF.sub.3).sub.2                                                        2-F                                                                               C.sub.3 H.sub.7                                                                    N                                                 108   5-OCH.sub.2 C(CH.sub.3)(CF.sub.3).sub.2                                                        2-F                                                                               C.sub.3 H.sub.7 -i                                                                 N                                                 109   5-OCH.sub.2 C(CF.sub.3).sub.3                                                                  2-F                                                                               C.sub.3 H.sub.7                                                                    N                                                 110   5-OCH.sub.2 C(CF.sub.3).sub.3                                                                  2-F                                                                               C.sub.3 H.sub.7 -i                                                                 N                                                 111   3-OCH.sub.2 C(CH.sub.3)(CF.sub.3).sub.2                                                        4-F                                                                               C.sub.3 H.sub.7                                                                    N                                                 112   3-OCH.sub.2 C(CH.sub.3)(CF.sub.3).sub.2                                                        4-F                                                                               C.sub.3 H.sub.7 -i                                                                 N                                                 113   3-OCH.sub.2 C(CF.sub.3).sub.2                                                                  4-F                                                                               C.sub.3 H.sub.7                                                                    N                                                 114   3-OCH.sub.2 C(CF.sub.3).sub.3                                                                  4-F                                                                               C.sub.3 H.sub.7 -i                                                                 N                                                 115   3-CH.sub.2 CH.sub.2 C(CH.sub.3).sub.3                                                          H  C.sub.4 H.sub.9 -i                                                                 N  1.5248                                         116   3-CH.sub.2 CH.sub.2 C(CH.sub.3).sub.3                                                          H  C.sub.5 H.sub.11 -i                                                                N  1.5222                                         117                                                                                   ##STR4##       H  C.sub.3 H.sub.7                                                                    CH 1.5301                                         118   3-OCH.sub.2 C(CH.sub.3).sub.3                                                                  H  C.sub.3 H.sub.7                                                                    CH 1.5339                                         119   3-CH.sub.2 CH.sub.2 C(CH.sub.3).sub.3                                                          H  CH.sub.3                                                                           N  1.5398                                         120   3-OC.sub.4 H.sub.9 -i                                                                          4-F                                                                               C.sub.3 H.sub.7 -i                                                                 N  44˜45                                    121   3-OC.sub.4 H.sub.9 -i                                                                          4-F                                                                               C.sub.3 H.sub.7                                                                    N  61˜63                                    122   5-CH.sub.2 CH.sub.2 CH(CH.sub.3)CH.sub.2 CH.sub.3                                              2-F                                                                               C.sub.4 H.sub.9 -i                                                                 N  1.5152                                         123   3-C.sub.2 F.sub.5                                                                              H  C.sub.3 H.sub.7 -i                                                                 N  1.5921                                         124   3-C.sub.3 F.sub.7                                                                              H  C.sub.3 H.sub.7 -i                                                                 N  1.4738                                         125   3-C.sub.4 F.sub.9                                                                              H  C.sub.3 H.sub.7 -i                                                                 N  1.4633                                         126   5-CH.sub.2 CH.sub.2 C(CH.sub.3).sub.3                                                          2-F                                                                               CH.sub.3                                                                           N                                                 127   5-CH.sub.2 CH.sub.2 C(CH.sub.3).sub.3                                                          2-F                                                                               C.sub.2 H.sub.5                                                                    N                                                 128   5-CH.sub.2 CH.sub.2 C(CH.sub.3).sub.3                                                          2-F                                                                               C.sub.4 H.sub.9 -i                                                                 N                                                 129   5-CH.sub.2 CH.sub.2 C(CH.sub.3).sub.3                                                          2-F                                                                               C.sub.4 H.sub.9 -t                                                                 N                                                 130   5-C(CH.sub.3).sub.3                                                                            2-F                                                                               C.sub.3 H.sub.7 -i                                                                 N                                                 131   5-C.sub.4 H.sub.9 -t                                                                           2-F                                                                               C.sub.3 H.sub.7 -i                                                                 N                                                 132   5-(CH.sub.2).sub.3 C(CH.sub.3).sub.3                                                           2-F                                                                               C.sub.3 H.sub.7 -i                                                                 N                                                 133   5-C.sub.4 H.sub.9 -t                                                                           2-F                                                                               C.sub.3 H.sub.7                                                                    N                                                 134   5-CH.sub.2 C(CH.sub.3).sub.3                                                                   2-F                                                                               C.sub.3 H.sub.7                                                                    N                                                 135   5-(CH.sub.2).sub.3 C(CH.sub.3).sub.3                                                           2-F                                                                               C.sub.3 H.sub.7                                                                    N                                                 136   3-CF.sub.2 CF.sub.2 CF(CF.sub.3).sub.2                                                         H  C.sub.3 H.sub.7                                                                    N                                                 137   3-CF.sub.2 CF.sub. 2 CF(CF.sub.3).sub.2                                                        H  C.sub.3 H.sub.7 -i                                                                 N  1.4498                                         138   3-CF(CF.sub.3).sub.2                                                                           H  C.sub.3 H.sub.7                                                                    N                                                 139   3-CF(CF.sub.3).sub.2                                                                           H  C.sub.3 H.sub.7 -i                                                                 N                                                 140   3-OCH.sub.2 Si(CH.sub.3).sub.3                                                                 H  C.sub.3 H.sub.7 -i                                                                 N  1.5310                                         141   3-OCH.sub.2 Si(CH.sub.3).sub.2 CH.sub.2 CH.sub.3                                               H  C.sub.3 H.sub.7 -i                                                                 N  1.5321                                         142   3-OCH.sub.2 Si(CH.sub.3).sub.2 CHCH.sub.2                                                      H  C.sub.3 H.sub.7 -i                                                                 N  1.5373                                         143   3-OCH.sub.2 Si(CH.sub.3).sub.2 CH.sub.2 Cl                                                     H  C.sub.3 H.sub.7 -i                                                                 N  1.5453                                         144   3-OCH.sub.2 Si(CH.sub.3).sub.3                                                                 H  C.sub.3 H.sub.7 -i                                                                 CH 1.5352                                         145   3-OCH(CH.sub.3)Si(CH.sub.3).sub.3                                                              H  C.sub.3 H.sub.7 -i                                                                 N  1.5252                                         146   3-OCH.sub.2 Si(CH.sub.3).sub.3                                                                 H  CH.sub.3                                                                           N  1.5430                                         147   3-OCH.sub.2 Si(CH.sub.3).sub.3                                                                 H  C.sub.2 H.sub.5                                                                    N  1.5385                                         148   3-OCH.sub.2 Si(CH.sub.3).sub.3                                                                 H  C.sub.4 H.sub.9                                                                    N  1.5248                                         149   3-OCH.sub.2 Si(CH.sub.3).sub.3                                                                 H  C.sub.4 H.sub.9 -s                                                                 N  1.5301                                         150   3-OCH.sub.2 Si(CH.sub.3).sub.3                                                                 H  C.sub. 4 H.sub.9 -t                                                                N  1.5216                                         151   3-OC.sub.2 H.sub.4 Si(CH.sub.3).sub.3                                                          H  C.sub.3 H.sub.7 -i                                                                 N  1.5288                                         152   5-OCH.sub.2 Si(CH.sub.3).sub.3                                                                 2-Cl                                                                              C.sub.3 H.sub.7 -i                                                                 N  1.5342                                         153                                                                                   ##STR5##       H  C.sub.3 H.sub.7 -i                                                                 N  49-51                                          154                                                                                   ##STR6##       H  C.sub.3 H.sub.7 -i                                                                 N  1.5499                                         155                                                                                   ##STR7##       H  C.sub.3 H.sub.7 -i                                                                 N  34-37                                          156                                                                                   ##STR8##       H  C.sub.3 H.sub.7 -i                                                                 N  1.5350                                         157                                                                                   ##STR9##       H  C.sub.3 H.sub.7 -i                                                                 N  1.5098                                         158                                                                                   ##STR10##      H  C.sub.3 H.sub.7 -i                                                                 N  1.5490                                         159                                                                                   ##STR11##      H  C.sub.3 H.sub.7 -i                                                                 N  1.5430                                         160                                                                                   ##STR12##      H  C.sub.3 H.sub.7 -i                                                                 N  1.5443                                         161                                                                                   ##STR13##      H  C.sub.3 H.sub.7 -i                                                                 N  1.5438                                         162   3-CH.sub.2 OC(CF.sub.3).sub.2 CH.sub.3                                                         H  C.sub.3 H.sub.7 -i                                                                 N  1.4821                                         163   3-CH.sub.2 OC(CH.sub.3).sub.2 CF.sub.3                                                         H  C.sub.3 H.sub.7 -i                                                                 N  1.5012                                         164   3-SCH.sub.2 CH(CH.sub.3).sub.2                                                                 H  C.sub.3 H.sub.7 -i                                                                 N  1.5551                                         165   3-SCH.sub.2 CH(CH.sub.3).sub.2                                                                 H  C.sub.3 H.sub.7 -i                                                                 CH 1.5675                                         166   3-C CC(CH.sub.3).sub.3                                                                         H  C.sub.3 H.sub.7 -i                                                                 N  1.5495                                         167   3-C CC(CH.sub.3).sub.3                                                                         4-F                                                                               C.sub.3 H.sub.7 -i                                                                 N  1.5431                                         168   3-CHCHC(CH.sub.3).sub.3                                                                        H  C.sub.3 H.sub.7 -i                                                                 N  1.5409                                         169   3-CHCHCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                      H  C.sub.3 H.sub.7 -i                                                                 N  1.5432                                         170   3-CHCHCH(CH.sub.3).sub.2                                                                       H  C.sub.3 H.sub.7 -i                                                                 N  1.5540                                         171   3-OCFCHBr          C.sub.3 H.sub.7 -i                                                                 N  1.5531                                         172   3-OCH.sub.2 Si(CH.sub.3).sub.3                                                                 H  C.sub.3 H.sub.7                                                                    N  1.5348                                         173                                                                                   ##STR14##      H  C.sub.3 H.sub.7 -i                                                                 N  1.5438                                         174   5-CH.sub.2 OC(CF.sub.3).sub.2 CH.sub.3                                                         2-F                                                                               C.sub.3 H.sub.7 -i                                                                 N  69-74                                          175   3-CH.sub.2 OC(CF.sub.3).sub.2 CH.sub.3                                                         2-F                                                                               C.sub.3 H.sub.7 -i                                                                 N  38-43                                          176                                                                                   ##STR15##      H  C.sub.3 H.sub.7 -i                                                                 N  1.5450                                         177                                                                                   ##STR16##      H  C.sub.3 H.sub.7                                                                    N  1.5477                                         178                                                                                   ##STR17##      H  C.sub.3 H.sub.7 -i                                                                 N  1.5428                                         179   5-CH.sub.2 OC(CF.sub.3).sub.3                                                                  2-F                                                                               C.sub.3 H.sub.7                                                                    N  1.4778                                         180                                                                                   ##STR18##      H  C.sub.3 H.sub.7                                                                    N  1.5478                                         181                                                                                   ##STR19##      2-F                                                                               C.sub.3 H.sub.7 -i                                                                 N  1.5345                                         182   3-CH.sub.2 OC(CF.sub.3).sub.3                                                                  4-F                                                                               C.sub.3 H.sub.7 -i                                                                 N  1.4772                                         183   3-CH.sub.2 OC(CF.sub. 3).sub.3                                                                 4-F                                                                               C.sub.3 H.sub.7                                                                    N  1.4788                                         184   3-C.sub.2 H.sub.4 Si(CH.sub.2).sub.3                                                           H  C.sub.3 H.sub.7                                                                    N  1.5289                                         185   3-C.sub.2 H.sub.4 Si(CH.sub.2).sub.3                                                           H  C.sub.3 H.sub.7 -i                                                                 N  1.5272                                         __________________________________________________________________________

The compounds according to the present invention can be produced by the following Methods A to D.

METHOD A (Scheme 1) ##STR20## wherein A is a halogen atom; and R, X, Y, and Z are the same as described above.

The compound represented by formula [I] can be produced by the reaction between the benzohydroximoylazole compound represented by formula [II] and the halogen compound represented by formula [III] in the presence of a base. In this reaction, the halogen compound or sulfonic ester compound may be employed in the amount of one or more equivalents. In addition, the base employed in the reaction includes an inorganic base, for example, an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, or the like; an alkali metal carbonate such as sodium carbonate, potassium carbonate, or the like; an alkali metal bicarbonate such as sodium bicarbonate, potassium bicarbonate, or the like, or an organic base such as triethylamine, N,N-dimethylaniline, pyridine, 1,8-diazacyclo[5,4,0] unde-7-cene, or the like.

The reaction can be carried out in the presence of a diluent, if necessary. The diluent includes water or inactive organic solvent. For example, a ketone such as acetone, butanone, or the like; an aromatic hydrocarbon which may be halogenated such as benzene, toluene, xylene, chlorobenzene, or the like; an aliphatic hydrocarbon such as petrolem ether, ligroin, or the like; an ether such as diethyl ether, tetrahydrofuran, dioxane, or the like; a nitrile such as acetonitrile, propionitrile, or the like; or an amide such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, or the like may be employed.

The synthesizing reaction temperature is set in the range of 0° C. to the reflux temperature of the reaction system, preferably in the range of 40° C. to 100° C. The reaction time depends on type of compound. The reaction may be usually completed for 1 hour to 6 hours.

METHOD B (Scheme 2) ##STR21## wherein B is a halogen atom, R, X, Y, and Z are the same as described above.

The compound represented by formula [I] can be produced by the reaction between the benzohydroximoylhalide compound represented by formula [IV] and the azole or triazole compound represented by formula [V] in the presence of a base. In this reaction, the azole or triazole compound can be employed in the amount of one or more equivalents with the base or the solvent. In addition, the same base as described in Method A can be employed.

The reaction can be carried out in the presence of an adequate dilute, if necessary. The same dilute as described above can be employed.

The synthesizing reaction temperature is set in the range of room temperature to the reflux temperature, preferably in the range of 80° C. to 130° C. The reaction time depends on type of compound. The reaction may be usually completed in 2 hours to 5 hours in a good yield.

METHOD C (Scheme 3) ##STR22## wherein D is a branched alkyl group having not fewer than 3 carbon atoms, a halogen-substituted alkyl group having not fewer than 3 carbon atoms, a substituted silylalkyl group, a cycloalkyl group which may be substituted with one or two alkyl groups, or a halogen-substituted alkenyl group; A' is a halogen atom, an alkylsulfonyloxy group, a benzenesulfonyloxy group which may be substituted, and X, Y, and Z are the same as described above.

The compound represented by formula [VIII] can be produced by the reaction between the compound having a hydroxide group on the benzene ring represented by formula [VI] and the halogen compound or sulfonate (ester) compound represented by formula [VII] in the presence of a base. In this reaction, the halogen compound or sulfonate (ester) compound can be employed in the amount of one or more equivalents. In addition, the same base as described in Method A can be employed.

The reaction can be carried out in the presence of an adequate dilute, if necessary. The same dilute as described above can be employed.

The synthesizing reaction temperature is set in the range of 0° C. to the reflux temperature of the reaction system, preferably in the range of 40° C. to 120° C. The reaction time depends on type of compound. The reaction may be usually completed in 1 hour to 8 hours.

METHOD D (Scheme 4) ##STR23## wherein E is a branched alkyl group having not fewer than 3 carbon atoms, a fluorine-substituted alkyl group having not fewer than 3 carbon atoms, a substituted silylalkyl group, a cycloalkyl group which may be substituted with one or two alkyl groups, or a halogen-substituted alkenyl group; X, Y, and Z are the same as described above.

The compound represented by formula [X] can be produced by a reaction between the compound having a hydroxide group on the benzene ring represented by formula [VI] and an alcoholic compound represented by formula [IX] in the presence of triphenylphosphine and diethyl azodicarboxylate or dimethyl azocarboxylate. In this reaction, the alcoholic compound can be employed in the amount of one or more equivalents.

The reaction can be carried out in the presence of an adequate dilute, if necessary. In addition, the same dilute as described in Method A can be employed. Preferably, acetonitrile or tetrahydrofuran is adequate.

The synthesizing reaction temperature is set in the range of 0° C. to the reflux temperature, preferably in the range of 30° C. to 120° C. The reaction time depends on type of compound. The reaction may be usually completed in 0.5 hours to 72 hours.

PREFERRED EMBODIMENTS OF THE INVENTION

The methods for producing the compounds according to the present invention will be concretely described in examples.

EXAMPLE 1

Synthesis of 1-[O-isopropyl-3-(3,3-dimethylbutoxy) benzohydroximoyl]-1H-1,2,4-triazole (Compound 19)

To a solution of 1.6 g (5.6 mmol) of 1-[3-(3,3-dimethylbutoxy)benzohydroximoyl]-1H-1,2,4-triazole dissolved in 100 ml of N,N-dimethylformamide was added 0.16 g (6.7 mmol) of sodium hydride. The mixture was stirred for 20 minutes at 80° C. And then allowed to sit and cool naturally to about 50° C. To the mixture was added 1.1 g (6.5 mmol) of 2-iodopropane and stirred for 1 hour at about 50° C. The reaction mixture was allowed to sit and cool naturally to room temperature. The cooled mixture was poured into water and extracted with ethyl acetate. After being washed with water, the organic layer was dried over anhydrous magnesium sulfate. The solvent in the organic layer was removed under reduced pressure. The residue was purified by column chromatography, thus obtaining 1.4 g (yield: 87%) of the desired product having a refractive index of [n_(D) ²⁰ ] 1.5289 at 20° C.

EXAMPLE 2

Synthesis of 1-(O-isopropyl-3-isopentylbenzohydroximoyl)-1H-1,2,4-triazole (Compound 9)

To 100 ml of N,N-dimethylformamide was added 1.5 g (5.6 mmol) of O-isopropyl-3-isopentylbenzohydroximoyl chloride, 0.8 g (11.6 mmol) of 1,2,4-triazole, and 1.6 g (11.6 mmol) of potassium carbonate. The mixture was stirred at 120° C. for 3 hours to complete the reaction. The reaction mixture was allowed to sit and cool naturally to room temperature. The cooled reaction mixture was poured into water and extracted with ethyl acetate. After being washed with water, the organic layer was dried over anhydrous magnesium sulfate. The solvent in the organic layer was then removed under reduced pressure. The residue was purified by column chromatography, thus obtaining 1.2 g (yield: 71%) of the desired product having a refractive index of [n_(D) ²⁰ ] 1.5317 at 20° C.

EXAMPLE 3

Synthesis of 1-(O-isopropyl-3-isopentylbenzohydroximoyl)-1H-1,2,4-triazole (Compound 3)

To 100 ml of N,N-dimethylformamide was added 1.2 g (4.9 mmol) of 1-(O-isopropyl-3-hydroxybenzohydroximoyl)-1H-1,2,4-triazole, 0.7 g (5.1 mmol) of isobutyl bromide, and 0.8 g (5.8 mmol) of potassium carbonate. The mixture was stirred for 1 hour at 80° C. to complete the reaction. The reaction mixture was allowed to sit and cool naturally. The cooled reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate. The solvent in the organic layer was then removed under reduced pressure. The residue was purified by column chromatography, thus obtaining 1.1 g (yield: 73%) of the desired produce having a refractive index of [n_(D) ²⁰ ] 1.5341 at 20° C.

[EXAMPLE 4]

Synthesis of 1-(O-isopropyl-3-isopentylbenzohydroximoyl)-1H-1,2,4-triazole (Compound 44)

2.5 g (0. 010M) of 1-(O-isopropyl-3-hydroxybenzohydroximoyl)-1H-1,2,4-triazole of, 0.9 g (10.0 mmol) of 2,2-dimethyl-1-propanol, and 2.6 g (10.0 mmol) of triphenylphosphine were dissolved in 40 ml of tetrahydrofuran. The solution was cooled to not more than 10° C. in a water bath. To the solution was added 1.7 g (10.0 mmol) of diethyl azodicarboxylate drop by drop so that the temperature of the solution was not over 20° C. The mixture was stirred overnight, and then heated to 60° C. The reaction mixture was then concentrated. The residue was purified by column chromatography, thus obtaining 0.8 g (yield: 25%) of the desired product having a refractive index of [n_(D) ²⁰ ] 1.5202 at 20° C.

EXAMPLE 5

Synthesis of 1-(O-isopropyl-3-isopentybenzohydroximoyl)-1H-1,2,4triazole (Compound 147)

1.5 g of 1-(3-trimethylsilylmethoxybenzohydroximoyl)-1H-1,2,4-triazole was dissolved in a mixed solvent of 50 ml of dried tetrahydrofuran (THF) and 50 ml of dimethylformamide (DMF). To the solution was added 0.15 g of sodium hydride, and the mixture was stirred for 10 minutes at room temperature. Ten ml of a THF solution dissolving 2.0 g of ethyl iodide was dropped into the mixture for 15 minutes. The reaction mixture was then stirred for 3 hours at 50° C. to complete the reaction. The resultant mixture was condensed in the half volume under reduced pressure. After the condensed mixture was allowed to sit and cool, it was poured into a large amount of water. The organic layer was extracted with ethyl acetate and dried over magnesium sulfate. The solvent of the organic layer was removed under reduced pressure. The residue was purified by column chromatography (eluate: hexane/ethyl acetate=4/1), thus obtaining 1.2 g (yield: 75%) of the desired product of having a refractive index of [n_(D) ²⁰ ] 1.5385 at 20° C.

EXAMPLE 6

Synthesis of 1-(O-isopropyl-3-isopentybenzohydroximoyl)-1H-1,2,4triazole (Compound 153)

3.3 g of O-isopropyl-3-cyclohexylbenzohydroximoyl chloride, 1.6 g of 1,2,4-triazole, and 3.3 g of potassium carbonate were dissolved in 100 ml of N,N-dimethylacetamide (DMAC). The mixture was stirred for 2 hours at 30° C. After the reaction mixture was allowed to sit and cool naturally, it was poured into water. The organic layer was extracted with ethyl acetate and dried over magnesium sulfate. The solvent in the organic layer was removed under reduced pressure. The residue was purified by column chromatography (eluate: hexane/ethyl acetate=4/1), thus obtaining 3.1 g (yield: 84%) of the desired product (white solid) of having a melting point of 49° C.˜51° C.

EXAMPLE 7

Synthesis of 1-(O-isopropyl-{3-(1,1,1,3,3,3-hexafluoro-2-methyl-2-propoxy)methyl}benzohydroximoyl]-1H-1,2,4-triazole (Compound 162)

1.2 g of O-isopropyl- {3-(1,1,1,3,3,3-hexafluoro-2-methyl-2-propoxy)methyl}benzohydroximoyl chloride, 0.4 g of 1,2,4-triazole, and 0.9 g of potassium carbonate were added to 50 ml of DMAC. The mixture was stirred at for 3 hours 130° C. After the resultant mixture was allowed to sit and cool naturally, it was poured into water. The organic layer was extracted with ethyl acetate and dried over magnesium sulfate. The solvent in the organic layer was removed under reduced pressure. The residue was purified by column chromatography (eluate: hexane/ethyl acetate=4/1), thus obtaining 0.9 g (yield: 69%) of the desired product (transparent viscous liquid) having a refractive index of [n_(D) ²⁰ ] 1.4821 at 20° C.

EXAMPLE 8

Synthesis of 1-(O-isopropyl-3-trimethylsilylmethoxybenzohydroximoyl)-1H-1,2,4-triazole (Compound 140)

2.7 g of 1-(O-isopropyl-3-hydroxybenzohydroximoyl)-1H-1,2,4-triazole, 1.5 g of chlorotrimethylsilane, 1.8 g of potassium carbonate, and a small amount of potassium iodide catalyst were added to 100 ml of DMF. The mixture was stirred for at 90° C. 2 hours. After the resultant mixture was allowed to sit and cool naturally, it was poured into water. The organic layer was extracted with ethyl acetate and dried over magnesium sulfate. The solvent in the organic layer was removed under reduced pressure. The residue was purified by column chromatography (eluate: hexane/ethyl acetate=4/1), thus yielding 3.2 g (yield: 89%) of the desired product (transparent viscous liquid) having a refractive index of [n_(D) ²⁰ ] 1.5310 at 20° C.

EXAMPLE 9

Synthesis of 1-(O-isopropyl-3-isopentylbenzohydroximoyl)-1H-1,2,4triazole (Compound 158)

2.0 g of 1-(O-isopropyl-3-hydroxybenzohydroximoyl)-1H-1,2,4-triazole, 1.6 g of cyclohexanol, and 4.3 g of triphenylphosphine were dissolved in 100 ml of THF. The mixture was maintained at about 5° C. To the solution was added 10 ml of a THF solution dissolving 2.8 g of diethyl azodicarboxylate drop by drop for 30 minutes. The mixture was stirred for 8 hours at room temperature. The solvent in the resultant mixture was removed under reduced pressure. The residue was purified by column chromatography (eluate: hexane/ethyl acetate=4/1), thus obtaining 2.1 g (yield: 78%) of the desired product (transparent viscous liquid) having a refractive index of [n_(D) ²⁰ ] 1.5490 at 20° C.

The compounds represented by formula [II], [IV], and [VI], which are raw materials of the compounds according to the present invention, can be produced in the Methods a to c.

METHOD a (Scheme 5) ##STR24## wherein R, X, Z, and B are the same as described above.

The benzohydroximoylazole compound represented by formula [II] can be synthesized by a reaction between a benzohydroximoylhalide compound represented by formula [XI] and an azole or triazole compound represented by the formula [IV], for example, in a solvent such as acetonitrile or the like in the presence of a base such as potassium carbonate or the like.

The synthesizing reaction temperature is see in the range of 0° C. to the reflux temperature of the reaction system, preferably 50° C. to 80° C. The reaction time depends on type of the compound. The reaction will usually be completed in 1 hour to 6 hours.

METHOD b (Scheme 6) ##STR25## wherein R, X, Z, and B are the same as described above.

The benzohydroximoylhalide compound represented by formula [IV] can be synthesized by reacting the benzamide compound represented by formula [XII] with the halogenation reagent such as phosphorus pentachloride, thionyl chloride, or the like in the presence or absence of an inactive solvent of an aromatic hydrocarbon such as benzene, toluene, or the like; a halogenated hydrocarbon such as chloroform, carbon tetrachloride, or the like. In addition, the benzohydroximoylhalide compound represented by formula [IV] can also be synthesized by reacting the benzamide compound represented by formula [XII] with the halogenation reagent comprising triphenyl phosphine and carbon tetrachloride, or triphenyl phosphine and carbon tetrabromide in the presence of an inactive solvent of a nitrile such as acetonitrile, propionitrile, or the like, or an aromatic hydrocarbon such as benzene, chlorobenzene, or the like. In this case, carbon tetrachloride and carbon tetrabromide can be employed as the solvent.

The synthesizing reaction temperature is set in the range of 0° C. to the reflux temperature of the reaction system, preferably 50° C. to 80° C. The reaction time depends on the type of compound. The reaction may be usually completed in 1 hour to 6 hours.

METHOD c (Scheme 7) ##STR26## wherein X, Y, and Z are the same as described above.

The compound represented by formula [VII] can be synthesized by hydrocracking the corresponding benzyloxy compound represented by formula [XIII] in the presence of a catalyst of carbon palladium in an inactive solvent of aprotic polar solvent, for example, water, acetic acid, an alcohol, an ethyl acetate, N,N-dimethylacetamide, N,N-dimethylformamide, or the like. In addition, the compound represented by formula [VI] can be also synthesized by debenzylating the corresponding benzyloxy compound represented by formula [XIII] using boron tribromide or boron trichloride in an inactive solvent of an aromatic hydrocarbon such as benzene, chlorobenzene, or the like, or a halogenated hydrocarbon such as dichloromethane, 1,2-dichloroethane, or the like.

The synthesizing reaction temperature is set in the range of -60° C. to 40° C., preferably -30° C. to room temperature. The reaction time depends on the type of compound. The reaction may be usually completed in 1 hour to 8 hours.

Furthermore, the compounds represented by formulae [XI], [XII], and [XIII] can be produced by the following methods:

The compound represented by formula [XI] can be synthesized by reacting the corresponding benzaldoxime, obtained by a reaction between the corresponding benzaldehyde compound and hydroxylamine hydrochloride using a known method, with a halogenation reagent such as N-bromosuccinimide, N-chlorosuccinimide, chlorine, or the like.

The compound represented by formula [XII] can be synthesized by reacting benzoylhalide or N-imidazylimidazole derived from the corresponding benzoic acid derivative with alkoxyamine.

In addition, the benzyloxy compound represented by formula [XIII] can be synthesized by the following successive steps of benzylating the hydroxy benzoic acid derivative; synthesizing halide benzoate from the benzylated compound in the known method; reacting the halide benzoate with alkoxyamine; halogenating it according to Method b; and carrying out the steps in Method B.

EXAMPLES

Next, the method for producing the raw materials according to the present invention will be described in detail with reference to the following examples.

Example 10

Synthesis of 1-[3-(3,3-dimethylbutoxy)benzohydroximoyl]-1H-1,2,4-triazole

To 100 ml of 1,2-dimethoxyethane were added 2.0 g (7.8 mmol) of 3-(3,3-dimethylbutoxy)benzohydroximoyl chloride, 1.9 g (27.5 mmol) of 1,2,4-triazole, and 1.5 g (10.9 mmol) of potassium carbonate. The mixture was stirred for 8 hours at about 50° C. After the resultant mixture was allowed to sit and cool naturally, the solvent in the mixture was removed. The residue was purified by column chromatography, thus obtaining the desired product of 1.2 g (yield: 46% ) .

Example 11

Synthesis of O-isopropyl-3-isopentylbenzohydroximoyl chloride

To 200 ml of acetonitrile were added 5.4 g (23.5 mmol) of O-isopropyl 3-isopentylbenzohydroxamic acid, 9.9 g (37.8 mmol) of triphenylphosphine, and 11.6 g (75.3 mmol) of carbon tetrachloride. The mixture was refluxed for 1 hour. The refluxed mixture was allowed to sit and cool naturally, and the solvent in the mixture was removed under reduced pressure. The residue was purified by column chromatography, thus obtaining the desired product of 5.1 g (yield: 88% ).

Example 12

Synthesis of 1-(O-isopropyl-3-hydroxybenzohydroximoyl)-1H-1,2,4 -triazole

To 150 ml of ethyl acetate were added 5.0 g of 1-(O-isopropyl-3-benzyloxybenzohydroximoyl )-1H-1,2,4-triazole (melting point: 62° C. to 67° C.) And 1 g of 10% palladium carbon at room temperature. In connection with the mixture, the hydrogenolysis reaction was carried out. After 8 hours, the palladium carbon was removed. The filtrate was then concentrated. The residue was purified by column chromatography, thus yielding 3.2 g (yield: 89%) of the desired product having a melting point of 160° C. to 163° C.

The insecticide according to the present invention includes the benzohydroximoylazole derivative represented by formula [I] as an active ingredient.

In the case where the compounds according to the present invention are employed as an insecticide, the compounds can be used alone or in combination with carriers, surfactants, dispersants, auxiliary agents, or the like, which are needed for formulation, and then formulated in a known manner, for example, into a dust, a wettable powder, an emulsifiable concentrate, fine particles, granules, or the like.

Suitable examples of carriers employed in the formulation are solid carriers such as zirclite, talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, siliceous sand, ammonium sulfate, and urea; and liquid carriers such as isopropyl alcohol, xylene, cyclohexanone, methylnaphthalene, and the like. Illustrative examples of the surfactants and dispersants include metal salts of alkylbenzenesulfonic acid and dinaphthylmethanedisulfonic acid, salts of alcohol sulfuric acid esters, alkylarylsulfonic acid salts, ligninesulfonic acid salts, polyoxyethylene glycol ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylenesorbitan monoalkylates, and the like.

Suitable examples of auxiliary agents include carboxymethylcellulose, polyethylene glycol, gum arabic, and the like.

These preparations can be applied directly, or after diluting the preparation to a suitable concentration.

The proportion of the active ingredient is selected as needed. When formulated into a dust or granules, 0.05% by weight to 20% by weight (preferably 0.1% by weight to 10% by weight) of the active ingredient is preferred. For an emulsifiable concentrate or wettable powder, 0.5% by weight to 80% by weight (preferably 1% by weight to 80% by weight) of the active ingredient is adequate.

The insecticide according to the present invention can be used for a number of purposes. For example, spraying of stem and leaf portions, injection into the irrigation water, and injection into the soil prior to seeding, at the time of seeding, at the time of transplantation, and during the maturation of the plant. The insecticide of the present invention also has fungicidal properties.

The rate of application of the insecticide according to the present invention may vary depending on the type of the active compound employed, the kind of the pest or disease to be controlled, the nature of occurrence of the pest or disease, the degree of damage, environmental conditions, the preparation form to be used, and the like.

When the insecticide of the present invention is applied directly in the form of dust or granules, it is recommended that the rate of application of the active ingredient be suitably chosen in the range of 0.05 g and 5 kg per 10 acres, preferably, in the range of 0.1 g and 1 kg per 10 acres. In addition, when the insecticide of the present invention is in the form of liquid such as an emulsifiable concentrate or a wettable powder, it is recommended that the rate of application of the active ingredient be suitably chosen in the range of 0.1 ppm and 5000 ppm, and preferably in the range of 1 ppm and 1000 ppm.

The insecticide according to the present invention can be employed alone or in combination with other insecticides or fungicides.

Next, the representative formulations are illustrated with reference to the following Formulation Examples, wherein all designations of "%" are given in "percent by weight". The kind and proportion of compounds and auxiliary agents are not restricted as described in the following examples.

Formulation Example 1: Emulsifiable concentrate

Thirty % of Compound (9), 20% of cyclohexanone, 11% polyoxyethylene alkylaryl ether, 4% of calcium alkylbenzenesulfonate, and 35% of methylnaphthalene were uniformly dissolved, thus obtaining an emulsifiable concentrate.

Formulation Example 2: Wettable powder

Forty % of Compound (10), 15% of diatomeceous earth, 15% of clay, 25% of white carbon, 2% of sodium dinaphtylmethanesulfonate, and 3% of sodium ligninsulfonate were uniformly mixed and ground into a wettable powder.

Formulation Example 3: Dust

Two % of Compound (17), 5% of diatomaceous earth, and 93% of clay were uniformly mixed and ground into a dust.

Formulation Example 4: Granules

Five % of Compound (1), 2% of sodium salt of the ester of lauryl alcohol, 5% of sodium ligninsulfonate, 2% of carbomethylcellulose, and 86% of clay were mixed and ground. One hundred parts by weight of the ground mixture was added to 20 parts by weight of water. The resulting mixture was kneaded and formed into granules of 14 mesh to 32 mesh by means of an extrusion granulator. The formed granules were then dried into the desired granules.

[Effect of the Invention]

The benzohydroximoylazole derivatives according to the present invention exhibit an improved control of harmful hemipterans such as Delphacidae including Nilaparavata lugens, Sogatella furcifera, Laodelphax striatellus or the like, Deltocephalidae including Nephotettix cincticeps, Empoasca onukii or the like, Aphididae including Aphis gossypii, Myzus persicae, Brevicoryne brassicae or the like, Aleyrodidae including Trialeurodes vaporareorum or the like, Pseudococcidae including Pseudococcus comstocki or the like, Pentatomidae including Leptocorixa corbetti or the like, in comparison with the compounds described in Japanese Patent Application First Publication No. 1-308260. In addition, the benzohydroximoylazole derivatives according to the present invention are effective to the harmful insects such as Lepidoptera including Plutella xylostella, Spodoptera litura, or the like, Diptera including Musca domestica, or the like, Coleopteraa including Lissorhoptrus oryzophilus, Callosobruchus chinesis, Aulacophora femoralis or the like, Orthoptera including Blattella germanica, or the like, Tetranychidae including Tetranychus urticae, Panonychus citri, or the like,

Furthermore, the compounds of the present invention exhibit fungicidal activities and are able to effectively control the pathogens which cause rice blast (Pyricularia oryzae) , rice sheath blight (Rhizoctonia solani), cucumber downy mildew (Pseudoperonospra cubensis), cucumber gray mold (Botrytis cinerea), cucumber powdery mildew (Sphaerotheca fuliginea) , Pseudomonas lachrymans, and Alternaria sooty spot of Chinese mustard (Altternaria brassicicola).

The effects of the compounds according to the present invention are now illustrated with reference to the following Test Examples.

Test Example 1

Mortality test of Neophotettix cincticeps exhibiting pesticide resistance to the commercially available reagents

The wettable powder prepared according to Formulation Example 2 was diluted with water to the concentration of 20 ppm. Into the aqueous preparation obtained, the stems and leaves of rice plants were dipped. After being air-dried, the stems and leaves were allowed to stand in a test tube. The 10 larvae of Neophotettix cincticeps were then added into the test tube, and the opening of the test tube was closed by absorbent cotton. After the closed test tube was placed in a thermostatic chamber at 25° C. for 6 days, the number of dead insects was counted and the percentage of dead insects was calculated. The results are shown in Table 2.

The test was then repeated. As comparative reagents, the compounds listed below, which are disclosed in Japanese Patent Application First Publication No. 1-308260, phenobcarb, and malathion were employed. The comparative tests were carried out in the concentration of 1000 ppm of the commercially available reagents.

Comparative compound 1

1-(O-ethyl-4-butylbenzohydroximoyl)-1H-1,2,4-triazole

Comparative compound 2

1-(O-isopropyl-4-butylbenzohydroximoyl)-1H-1,2,4-triazole

Comparative compound 3

1-(O-isopropyl-4-butoxybenzohydroximoyl)-1H-1,2,4triazole

Comparative compound 4

1-(O-isopropyl-4-hexylbenzohydroximoyl)-1H-1,2,4triazole

Comparative compound 5

1-(O-propyl-3-(2,2,2-trifluoroethoxybenzohydroximoyl)-1H-1,2,4-triazole

Comparative compound 6

1-(O-isopropyl-2-chloro-5-methoxybenzohydroximoyl)-1H-1,2,4-triazole

Comparative compound 7

Phenobcarb (common name, produced by Kumiai Chemical Industries, Co., Ltd.)

Comparative compound 8

Malathion (common name, produced by Kumiai Chemical Industries, Co., Ltd.)

                  TABLE 2                                                          ______________________________________                                         Compound No.        Dead Insects (%)                                           ______________________________________                                          1                  100                                                         2                  100                                                         3                  100                                                         4                  100                                                         5                  100                                                         6                  100                                                         7                  100                                                         8                  100                                                         9                  100                                                         10                 100                                                         11                 100                                                         12                 100                                                         13                 100                                                         14                 100                                                         15                 100                                                         16                 100                                                         17                 100                                                         18                 100                                                         19                 100                                                         20                 100                                                         21                 100                                                         22                 100                                                         23                 100                                                         24                 100                                                         25                 100                                                         26                 100                                                         27                 100                                                         28                 100                                                         29                 100                                                         30                 100                                                         31                 100                                                         32                 100                                                         33                 100                                                         34                 100                                                         35                 100                                                         36                 100                                                         37                 100                                                         38                 100                                                         39                 100                                                         40                 100                                                         41                 100                                                         42                 100                                                         43                 100                                                         44                 100                                                         45                 100                                                         46                 100                                                         47                 100                                                         48                 100                                                         49                 100                                                         50                 100                                                         51                 100                                                         52                 100                                                         53                 100                                                         54                 100                                                         55                 100                                                         56                 100                                                         57                 100                                                         58                 100                                                         59                 100                                                         60                 100                                                         61                 100                                                         62                 100                                                          63                100                                                         64                 100                                                         65                 100                                                         66                 100                                                         67                 100                                                         68                 100                                                         69                 100                                                         70                 100                                                         71                 100                                                         72                 100                                                         73                 100                                                         74                 100                                                         75                 100                                                         76                 100                                                         77                 100                                                         78                 100                                                         79                 100                                                         80                 100                                                         81                 100                                                         82                 100                                                         83                 100                                                         84                 100                                                         85                 100                                                         86                 100                                                         87                 100                                                         88                 100                                                         89                 100                                                         90                 100                                                        115                 100                                                        116                 100                                                        117                 100                                                        118                 100                                                        119                 100                                                        120                 100                                                        121                 100                                                        122                 100                                                        123                 100                                                        124                 100                                                        125                 100                                                        Comparative compound 1                                                                              30                                                        Comparative compound 2                                                                              60                                                        Comparative compound 3                                                                              50                                                        Comparative compound 4                                                                              40                                                        Comparative compound 5                                                                              30                                                        Comparative compound 6                                                                              20                                                        Comparative compound 7                                                                              30                                                        (Commercially available reagent)                                               Comparative compound 8                                                                              40                                                        (Commercially available reagent)                                               ______________________________________                                    

Test Example 2

Mortality test of Nilaparavata lugens

The wettable powder prepared according to Formulation Example 2 was diluted with water to the predetermined concentration. Into the aqueous preparation obtained, the stems and leaves of the rice plant were dipped. After being air-dried, the stems and leaves were allowed to stand in a test tube. The 10 larvae of Nilaparavata lugens were added into the test tube, and the opening of the test tube was closed by the absorbent cotton. After the closed test tube was placed in a thermostatic chamber at 25° C. for 6 days, the number of dead insects was counted and the percentage of dead insects was calculated. The results are shown in Table 3.

The same comparative compounds as described in Test Example 1 were employed.

                  TABLE 3                                                          ______________________________________                                                           Dead Insects (%)                                             Compound No.        20 ppm  4 ppm                                              ______________________________________                                          1                  100     100                                                 2                  100     100                                                 3                  100     100                                                 4                  100     100                                                 5                  100     100                                                 6                  100     100                                                 7                  100     100                                                 8                  100     100                                                 9                  100     100                                                 10                 100     100                                                 11                 100     100                                                 12                 100     100                                                 13                 100     100                                                 14                 100     100                                                 15                 100     100                                                 16                 100     100                                                 17                 100     100                                                 18                 100     100                                                 19                 100     100                                                 20                 100     100                                                 21                 100     100                                                 22                 100     100                                                 23                 100     100                                                 24                 100     100                                                 25                 100     100                                                 26                 100     100                                                 27                 100     100                                                 28                 100     100                                                 29                 100     100                                                 30                 100     100                                                 31                 100     100                                                 32                 100     100                                                 33                 100     100                                                 34                 100     100                                                 35                 100     100                                                 36                 100     100                                                 37                 100     100                                                 38                 100     100                                                 39                 100     100                                                 40                 100     100                                                 41                 100     100                                                 42                 100     100                                                 43                 100     100                                                 44                 100     100                                                 45                 100     100                                                 46                 100     100                                                 47                 100     100                                                 48                 100     100                                                 49                 100     100                                                 50                 100     100                                                 51                 100     100                                                 52                 100     100                                                 53                 100     100                                                 54                 100     100                                                 55                 100     100                                                 56                 100     100                                                 57                 100     100                                                 58                 100     100                                                 59                 100     100                                                 60                 100     100                                                 61                 100     100                                                 62                 100     100                                                 63                 100     100                                                 64                 100     100                                                 65                 100     100                                                 66                 100     100                                                 67                 100     100                                                 68                 100     100                                                 69                 100     100                                                 70                 100     100                                                 71                 100     100                                                 72                 100     100                                                 73                 100     100                                                 74                 100     100                                                 75                 100     100                                                 76                 100     100                                                 77                 100     100                                                 78                 100     100                                                 79                 100     100                                                 80                 100     100                                                 81                 100     100                                                 82                 100     100                                                 83                 100     100                                                 84                 100     100                                                 85                 100     100                                                 86                 100     100                                                 87                 100     100                                                 88                 100     100                                                 89                 100     100                                                 90                 100     100                                                 91                 100     100                                                115                 100     100                                                117                 100     100                                                118                 100     100                                                119                 100     100                                                120                 100     100                                                121                 100     100                                                122                 100     100                                                Comparative compound 1                                                                              90      50                                                Comparative compound 2                                                                              90      70                                                Comparative compound 3                                                                              90      70                                                Comparative compound 4                                                                              60      30                                                Comparative compound 5                                                                              90      50                                                Comparative compound 6                                                                             100      70                                                ______________________________________                                    

Test Example 3

Mortality test of Aphis gossypii

The wettable powder prepared according to Formulation Example 2 was diluted with water to the concentration of 100 ppm. Into the aqueous preparation obtained, seedlings of the cucumber plant were dipped. After being air-dried, they were allowed to stand in a polyethylene cup having a diameter of 55 mm. Ten larvae of Aphis gossypii were put on the leaves of the seedlings in the cup. After the cup was placed in a thermostatic chamber at 25° C. for 3 days, the number of dead insects was numbered and the percentage of dead insects was calculated. The test was then repeated. The results are shown in Table 4.

                  TABLE 4                                                          ______________________________________                                         Compound No.   Dead Insects (%)                                                ______________________________________                                          1             100                                                              2             100                                                              3             100                                                              4             100                                                              5             100                                                              6             100                                                              7             100                                                              8             100                                                              9             100                                                              10            100                                                              11            100                                                              12            100                                                              13            100                                                              14            100                                                              15            100                                                              16            100                                                              17            100                                                              18            100                                                              19            100                                                              20            100                                                              21            100                                                              22            100                                                              23            100                                                              24            100                                                              25            100                                                              26            100                                                              27            100                                                              28            100                                                              29            100                                                              30            100                                                              31            100                                                              32            100                                                              33            100                                                              34            100                                                              35            100                                                              36            100                                                              37            100                                                              38            100                                                              39            100                                                              40            100                                                              41            100                                                              42            100                                                              43            100                                                              44            100                                                              45            100                                                              46            100                                                              47            100                                                              48            100                                                              49            100                                                              50            100                                                              51            100                                                              52            100                                                              53            100                                                              54            100                                                              55            100                                                              56            100                                                              57            100                                                              58            100                                                              59            100                                                              60            100                                                              61            100                                                              62            100                                                               63           100                                                              64            100                                                              65            100                                                              66            100                                                              67            100                                                              68            100                                                              69            100                                                              70            100                                                              71            100                                                              72            100                                                              73            100                                                              74            100                                                              75            100                                                              76            100                                                              77            100                                                              78            100                                                              79            100                                                              80            100                                                              81            100                                                              82            100                                                              83            100                                                              84            100                                                              85            100                                                              86            100                                                              87            100                                                              88            100                                                              89            100                                                              90            100                                                              91            100                                                             115            100                                                             117            100                                                             118            100                                                             119            100                                                             ______________________________________                                    

Test Example 4

Mortality test of Nilapara lugens

The wettable powder prepared according to Formulation Example 2 was diluted with water to the predetermined concentration. Into the aqueous preparation obtained, the stems and leaves of rice plants were dipped. After being air-dried, the stems and leaves were allowed to stand in a test tube. Ten larvae of Nilapara lugens were added into the test tube, and the opening of the test tube was closed by absorbent cotton. After the closed test tube was placed in a thermostatic chamber at 25° C. for 6 days, the number of dead insects was counted and the percentage of dead insects was calculated. The test was then repeated. The results are shown in Table 5.

                  TABLE 5                                                          ______________________________________                                                        Dead Insects (%)                                                Compound No.     20 ppm  4 ppm                                                 ______________________________________                                         140              100     100                                                   141              100     100                                                   142              100     100                                                   143              100     100                                                   144              100     100                                                   145              100     100                                                   146              100     100                                                   147              100     100                                                   148              100     100                                                   149              100     100                                                   150              100     100                                                   151              100     100                                                   152              100     100                                                   153              100     100                                                   154              100     100                                                   155              100     100                                                   156              100     100                                                   157              100     100                                                   158              100     100                                                   159              100     100                                                   160              100     100                                                   161              100     100                                                   162              100     100                                                   163              100     100                                                   164              100     100                                                   165              100     100                                                   166              100     100                                                   167              100     100                                                   168              100     100                                                   169              100     100                                                   170              100     100                                                   171              100     100                                                   172              100     100                                                   173              100     100                                                   174              100     100                                                   175              100     100                                                   176              100     100                                                   177              100     100                                                   178              100     100                                                   179              100     100                                                   180              100     100                                                   181              100     100                                                   182              100     100                                                   183              100     100                                                   184              100     100                                                   185              100     100                                                   ______________________________________                                    

Test Example 5

Mortality test of Nephotettix cincticeps exhibiting pesticide resistance to the commercially available reagents

The wettable powder prepared according to Formulation Example 7 was diluted with water to the concentration of 100 ppm. Into the aqueous preparation obtained, the stems and leaves of rice plants were dipped. After being air-dried, the stems and leaves were allowed to stand in a test tube. Five larvae of Nephotettix cincticeps were added into the test tube, and the opening of the test tube was closed by absorbent cotton. After the closed test tube was placed in a thermostatic chamber at 25° C. for 6 days, the dead insects were counted and the percentage of dead insects was calculated. The test was then repeated. The results are shown in Table 6.

                  TABLE 6                                                          ______________________________________                                         Compound No.   Dead Insects (%)                                                ______________________________________                                         140            100                                                             141            100                                                             142            100                                                             143            100                                                             144            100                                                             145            100                                                             146            100                                                             147            100                                                             148            100                                                             149            100                                                             150            100                                                             151            100                                                             152            100                                                             154            100                                                             155            100                                                             156            100                                                             157            100                                                             158            100                                                             159            100                                                             160            100                                                             161            100                                                             162            100                                                             163            100                                                             164            100                                                             165            100                                                             166            100                                                             167            100                                                             168            100                                                             169            100                                                             170            100                                                             171            100                                                             172            100                                                             173            100                                                             174            100                                                             175            100                                                             176            100                                                             177            100                                                             178            100                                                             179            100                                                             180            100                                                             181            100                                                             182            100                                                             183            100                                                             184            100                                                             185            100                                                             ______________________________________                                    

Test Example 6

Mortality test of Aphis gossypii

The wettable powder prepared according to Formulation Example 2 was diluted with water to the concentration of 100 ppm. Into the aqueous preparation obtained, seedlings of the cucumber plant were dipped. After being air-dried, they were allowed to stand in a polyethylene cup having a diameter of 55 mm. Ten larvae of Aphis gossypii were put on the leaves of the cucumber plant. After the cup was placed in a thermostatic chamber at 25° C. for 3 days, the dead insects were counted and the percentage of dead insects was calculated. The test was then repeated. The results are shown in Table 7.

                  TABLE 7                                                          ______________________________________                                         Compound No.   Dead Insects (%)                                                ______________________________________                                         140            100                                                             141            100                                                             143            100                                                             144            100                                                             145            100                                                             146            100                                                             147            100                                                             148            100                                                             149            100                                                             150            100                                                             151            100                                                             152            100                                                             153            100                                                             154            100                                                             155            100                                                             156            100                                                             157            100                                                             158            100                                                             159            100                                                             160            100                                                             161            100                                                             162            100                                                             163            100                                                             164            100                                                             165            100                                                             166            100                                                             167            100                                                             168            100                                                             169            100                                                             170            100                                                             171            100                                                             172            100                                                             173            100                                                             174            100                                                             175            100                                                             176            100                                                             177            100                                                             178            100                                                             179            100                                                             180            100                                                             181            100                                                             182            100                                                             183            100                                                             184            100                                                             185            100                                                             ______________________________________                                     

What is claimed is:
 1. A benzohydroximoylazole compound having the formula: ##STR27## wherein R is a branched C₅₋₈ alkyl group, a fluorine-substituted C₂₋₆ alkyl group, a branched C₃₋₇ alkoxy group, a halogen-substituted C₃₋₇ alkoxy group, a C₃₋₇ cycloalkyl group, a C₄₋₇ cycloalkylmethyl group which may be substituted with one or two methyl groups, a trimethylsilylethyl group, a silyl C₁₋₂ alkoxy group which is trisubstituted with, independently, methyl, ethyl, chloromethyl or vinyl groups, a C₃₋₆ cycloalkoxy group which may be substituted with one or two methyl groups, a butylthio group, a halogen-substituted C₄₋₅ alkoxymethyl group, a C₅₋₆ alkenyl group, a C₆ alkynyl group, or a halogen-substituted vinyloxy group;X is a hydrogen atom, a chlorine atom or a fluorine atom; Y is a C₁₋₄ alkyl group; and Z is a nitrogen atom.
 2. The benzohydroximoylazole compound of claim 1, wherein R is a branched C₅₋₈ alkyl group, a fluorine-substituted C₂₋₆ alkyl group, a branched C₃₋₇ alkoxy group or a halogen-substituted C₃₋₇ alkoxy group, a C₅₋₆ cycloalkyl group, a C₅₋₆ cycloalkylmethyl group which may be substituted by one or two methyl groups, a C₅₋₆ cycloalkoxy group which may be substituted with one or two methyl groups.
 3. The benzohydroximoylazole compound of claim 1, wherein R is a branched C₅₋₈ alkyl group, a fluorine-substituted C₂₋₆ alkyl group, a branched C₅₋₇ alkoxy group or a halogen-substituted C₃₋₇ alkoxy group.
 4. The benzohydroximoylazole compound of claim 1, wherein R is a branched C₅₋₈ alkyl group or a branched C₅₋₇ alkoxy group.
 5. The benzohydroximoylazole compound of claim 1, wherein R is a member selected from the group consisting of --OCH₂ Si(CH₃)₃, --OCH₂ Si(CH₃)₂ CH₂ CH₃, --OCH₂ Si(CH₃)₂ CH═CH₂, --OCH₂ Si(CH₃)₂ CH₂ Cl, --OCH(CH₃)Si(CH₃)₃, --OC₂ H₄ Si(CH₃)₃, --CH₂ OC(CH₃)₂ CF₃, --SCH₂ CH(CH₃)₂, --C.tbd.CC(CH₃)₃, --CH═CHC(CH₃)₃, --CH═CHCH₂ CH₂ CH₂ CH₃ , --CH═CHCH(CH₃)₂, --OCF═CHBr, --CH₂ OC(CF₃)₂ CH₃, --CH₂ OC(CF₃)₃, --C₂ H₄ Si(CH₃)₃, ##STR28##
 6. The benzohydroximoylazole compound of claim 1, wherein R is in the 3-position or 5-position of the phenyl ring of said compound.
 7. The benzohydroximoylazole compound of claim 1, wherein R is a C₄₋₇ cycloalkylmethyl group.
 8. The benzohydroximoylazole compound of claim 5, wherein R is in the 3-position or 5-position of the phenyl ring of said compound.
 9. An insecticidal composition comprising an insecticidally effective amount of the benzohydroximoylazole compound of claim 1 and an acceptable carrier.
 10. An insecticidal composition comprising an insecticidally effective amount of the benzohydroximoylazole compound of claim 2 and an acceptable carrier.
 11. An insecticidal composition comprising an insecticidally effective amount of the benzohydroximoylazole compound of claim 3 and an acceptable carrier.
 12. An insecticidal composition comprising an insecticidally effective amount of the benzohydroximoylazole compound of claim 5 and an acceptable carrier.
 13. An insecticidal composition comprising an insecticidally effective amount of the benzohydroximoylazole compound of claim 6 and an acceptable carrier. 